Sulphide dyestuffs from azines and process of making



TPatented Oct. 14, 1930 uNiTE-D. STATES PATENT OFFICE autmqwimm Porno]?HUDDERSFIELID, AND MAX WYLER, or BLA K EY, tram onnsmnn, ENGLAND,AssIeNoRs TO IMPERIAL CHEMICAL mnusrnrns LIMITED,

or rioicr ioiv, ENGLAND 'SULPHIDE 'nrnstrurrsrnom AZINES AND PROCESS orMaximo No was; Application filed my 19, 1928, Serial No. 294,051,111111in Great Britain September 8, i927.

" 4 This invention relatesto new intermediate compounds and tonewred-brownsulphide vat, dyes,obtainabletherefrom by the usual processesof thionation.

It is Well knownthat certain hydroxylated "derivatives ofnphenazine, e.g, 'aminohydro zyphena zine henthionated by means of sodium'polysulphideainthe presence of copper com- :p'ounds,z -sulphide vat"dyes giving reddish brown shadeson cotton.

We have "now found-by treating certain Y 1 nuclear hydroXy-lateddyes ofthe azine group,

' phenazines, naphthophenaz'ines or dinaph- 'rthazines, With alkalimetalhydroxide and namelythe class of compounds consisting of carbon dioxideunder pressure, either separately or combined as alkali metalbicarbongate, :wezt. obtained "dyestufi' intermediates which areprobably modilied carboxylated For the practice of"ur"invention We mayuse as starting material any hydroxylated Vphenazine, ,naphthophenazineor dinaph- '.thazinein vvhichthere is a free position ortho to at leastone hydroxyl group. The treatment; may be; carried out in aqueous media,,,e. ;g.when};using an alkali'metal bicarbonate a for-carbon dioxidegas, orin the absence of o-vvat'er," e; g. when-using carbon dioxidegas.

The ya-lkali' metal salt of-thehydroxycompound maybe employed;

treatment is the first step in our proc- .-ess"and forms the dyestufiintermediate which is subsequentlyithionated, The exact course ofreaction is not known. It isprobablethat "a carboxylationtakes place ina manner analogous' to that; in ;Kolbes synthesis (saliwcylici acidfrom; sodium "-phenolate) and this carboxylation :mayjxor .may not beaccom- *pani'ed:by'anhydrideformationorv by some 9 typeiof-condensation. Itisdiflicult to estabnula Y lish chemically theexact constitution of the I I intermediate so produced. However we havefound that the intermediate so produced is different from azinesof thesame type con taining a carboxylic group and made in other ways; andthat the sulphidevat dyes pro duced by subsequently thionating thisintermediate product are different from those heretofore .known and,have advantageous properties. l/Ve shall for convenience term these newdyestuif intermediates,modified carboxylated, hydroxylated azines.

The starting material may contain other substituents besides theessential hydroxyl group, and we obtain especially good results withazines containing bothamino and hydroxyl groups. I j I a The modifiedcarboxylated hydroirylated azines are red or reddish-brown in colour,almost insoluble inwater, dilute mineral acids and sodium carbonatesolution but readily dissolving in an aqueous solution of caustic sodato a brown solution. 7, j

The sulphide dyes are green substances nearly insoluble in waterbutdissolving readily in dilute sodium sulphide solution, dye- I ing cottonin brown shades. I i- Our invention is illustrated, but not limited, bythe following examples, in which the parts are by weight: M I Y Eocamplel. parts of the sodium salt of the azine.representedby the followingforare dissolved in '50 parts water: and 160 parts v sodium bicarbonate"are added; The mixture is heated in a suitable vessel under its ownpressure to a temperature of 135 for 10 hours. After cooling, solublesodium salts are removed by washing and filtration and the sodium saltof the new modified carboxylated fazine remains behind. This can bereadily converted into the acidic form by treatment with an acid, as,for instance, dilute hydrochloric acid. The acidic form is a brightreddish powder which is insoluble in watenbut 5 dissolyes readily incaustic alkalies to form a brown solution. 1 v

I By thionation with sodium polysulphide in the presence of coppersulphate a reddishbrown sulphide vatdye is obtained. The dyestufi isadark green-substance with bright tracture nearly insoluble in water butdissolving readily in dilute sodium sulphide solution.

' Cotton dyed insuch a solution gives brown shades 'which,""on standingin the wet state in air, develop a bright red-brown shade of goodfastnessto-li-ght.

' Ema'mple 711E "arts of the finely-divided sodium-salt of the azi erepresented by';. h

following formula tained for12 hours when the vessel is allowed to cool,The dry powdery product resulting can be used directly for] makingsulphur colours or'can be converted into theacidic form as described inExampleI. v

What we claim and desire to secure by Let ters Patent is 1. In themanufacture of sulphide dyes, the process which comprises treating underpressure theclass o1": azine compounds conslsting of phenazines,naphthophenazines and dinaphthaz ines with alkali metal hydroxide andcarbon dioxide to produce modified carboxylated hydroxylated azinesandthen thi- ,onating the so produced modified azines by means o-fanalkali metal polysulphide in the presence of acopper compound.

2. In the manufacture of sulphide dyes, the process which comprisestreating under pressure the class of azine compounds consisting ofphen'azines,naphthophenazines and dinaphthazines with alkali metalhydroxide and carbon dioxide toproduce modified car- 'boxylatedhydroxylated azines and then thionating the so produced modified azinesby means of sodium polysulphide in thepresence of a copper compound.

f '3. In the manufacture of sulphide dyes,

the process which comprises treating under pressure anuclearhydroxylated phenazine withalkali metal hydroxide and carbon di-'oxide and thionating the resulting product with analkalimetalpolysulphide in the presence of a'copper compound. V 4.In-the'm'anufacture otsulphidedyes, the

process which comprises treating under pressure a nuclear hydroxylatedphenazine with alkali metal hydroxide and carbon dioxide combined as analkali metal bicarbonate and thionatingthe resulting product with an allneman polysu-lphide intheipresence of a copperecompound.

5.7In the manufactureof sulphide dyes, I.

the process which comprises treatment under pressure of a nuclear;hydroxylated phenazine with alkali met'al'hydroxide and carbondioxideand thionating the resulting product with sodium pei'yui'phide iffthepresence of arqopperfloll pol nd: r 6. In the manufacture of sulphidedyes,

the process which compri'ses treatment under pressure of a nuclearhydro'xylatedfphenazinewith alkali and carbon dioxide combined as analkali metal bicarbonateand thionating the resulting product with sodiumpolysulphide in the presenceof a copper com= pound.

7. In the manufactureof sulphide dyes, the process which comprisestreatment un-f der pressureofa nuclear hydroxylated phenazine withalkali metal hydroxide and car-' bon dioxide combined as an alkali metalbi; carbonate and thionating the .resultingilprodnot with sodiumsulphide and sulphur in the presence of a coppercompound.

process which comprises treatment under pressure of anuclear-hydroxylated phenazine with alkali metalhydroxide. and car; zbondioxide and thionating the zresulting product. with sodium sulphide and.sulphur intheypresence ofa coppermoxider 9, In the manufacture of.sulphide the process which comprisestreating .under pressure .an azinecompound having the following structure HN on--" s.

'with'a-lkali metal hydroxide and carbon dioxide and then thionatingthe:resulting' product ence of copper sulphate.

with an alkali metal polysulphideinthepres- I 10. As new productsythesulphide d yejstuils obtainable by treating under pressure the class ofazinecompound'sconsisting of phenazines, naphthophenazinesand'dinaphthazines withalkali-metal hydroxide andcar- 120 bon dioxide toproduceimodified carboxylated hydroxylated a'zi-nes and-then thionatingthe so produced modified azinesby means of an.

alkali metal polysulphide inthe presence ofa copper compound, the said-dyeStuiisLbeing dark powders nearly insolublein water but dissolvingreadily in dilute sodium sulphide solution and dyeing cotton in brownshades.

11. vAs a new product, the sulphide jdyestuff obtainable by treatingunder I pressure a nuclear hydroxylated Lphenazine ,withgall- "i so i g8. In the manufacture of sulphidedyes,.the

. kali metal hydroxide and carbon dioxide and thionating the resultingproduct with an alkali metal poly'sulphide in the presence of a coppercompound, the said dyestuff being a dark powder nearly insoluble inwater but dissolving readily in dilute sodium sulphide solution anddyeing cotton in brown shades.

7.12. As a new product, the sulphide dyestufi' obtainable by treatingunder pressure a nuclear hydroxylated phenazine with alkali metalhydroxide and carbon dioxide and thionating the resulting product withan alkali metal polysulphidein the presence of a copper compound, thesaid dyestufi being a dark green powder nearly insoluble in water butdissolving readily in dilute sodium sulphide solution and dyeing cottonin brown shades. In testimony whereof we ailix our signatures. v

' RUPERT W. POPE.

f-MAX WYLER

